US5540840A - Use of fluidized bed reactors for treatment of wastes containing organic nitrogen compounds - Google Patents
Use of fluidized bed reactors for treatment of wastes containing organic nitrogen compounds Download PDFInfo
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- US5540840A US5540840A US08/458,946 US45894695A US5540840A US 5540840 A US5540840 A US 5540840A US 45894695 A US45894695 A US 45894695A US 5540840 A US5540840 A US 5540840A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/08—Aerobic processes using moving contact bodies
- C02F3/085—Fluidized beds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/903—Nitrogenous
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/903—Nitrogenous
- Y10S210/904—-CN containing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/908—Organic
Definitions
- the present invention relates to treatment of waste streams containing organic nitrogen compounds, and more particularly to ammonification of such streams by microbial degradation in a fluidized bed reactor.
- Nitriles including mono-nitriles and dinitriles, are recognized as troublesome contaminants of waste water streams. Dinitriles, such as fumaronitrile and succinonitrile, are especially notorious for their acute toxicity and resistance to degradation. Note, for example, European patent application no. 87310689.2, publication no. 0 274 856, of Knowles. Moreover, degradation of dinitriles produces twice as much ammonia as does degradation of nitriles. The ammonia production has been viewed as a serious problem due to its toxicity and effects on pH.
- Organic nitrogen compounds are found in many types of waste streams, often as by products in synthesis of organic compounds.
- acrylonitrile (AN) is produced by an ammoxidation process in which propylene and ammonia are catalytically combined.
- by-products such as succinonitrile, fumaronitrile and maleonitrile are formed and end up in the stripper bottoms and so in the waste water along with some of the acrylonitrile.
- the waste water contains ammonium salts and organic acids as well.
- a typical waste water stream from acrylonitrile production may include hydrogen cyanide, acetonitrile, acrolein, acrylonitrile, oxazole, propionitrile, methacrylonitrile, acetic acid, c-crotononitrile, allyl cyanide, t-crotononitrile, acrylic acid, cyanobutene, cyanobutadiene, pyrazine, cyanobutadiene, maleonitrile, fumaronitrile, cyanofuran, cyanopentadiene, cyclopentadiene, cyanopropanal, acrylamide, succinonitrile, maleimide, benzonitrile, cyanopyridine, methylbenzonitrile and cyanopentene, among others.
- waste water containing organic nitrogen compounds is produced during the production of other nitrogen-containing compounds.
- ammonia levels of about 300 mg/l or more, especially about 500 mg/l or more, are troublesome unless the medium is buffered.
- Fluidized bed reactors utilizing immobilized bacteria technology (IBT) contain a fluidized bed of particulate solids as a biocarrier supporting microorganisms capable of biodegrading certain compositions. FBRs achieve expansion of the biocarrier bed by recycling the waste water being treated upward through the reactor.
- Use of FBRs employing IBT has been reported in certain waste water treatment processes.
- U.S. Pat. No. 4,009,099 to Jeris describes a method for treating waste water with an FBR using IBT.
- that patent describes the use of an FBR for converting ammonia nitrogen in waste water to an oxidized form.
- the patent is not directed to degradation of organic nitrogen compounds to ammonia, but to nitrification of ammonia to NO 3 , which would then require denitrification. Thus, it is not applicable to treatment of nitrile streams.
- the present invention is directed to a novel method for treatment of a liquid waste stream containing water and a concentration of organic nitrogen compounds of at least about 300 TKN.
- the method comprises several steps. First, the liquid waste stream is oxygenated to produce an oxygenated liquid containing water and the organic nitrogen compounds. Next, the oxygenated liquid is passed through a fluidized bed reactor containing a fluidized bed of nitrile-absorbing particulate solids supporting microorganisms capable of biodegrading the organic nitrogen compounds, thereby to subject the organic nitrogen compounds in the oxygenated liquid to aerobic microbial degradation and to produce an effluent containing water, ammonia and carbon dioxide. The pH of the bioreactor and the effluent is maintained between about 6 and about 8.
- the provision of a method of improved efficacy for treating aqueous waste streams containing organic nitrogen compounds may be noted the provision of a method of improved efficacy for treating aqueous waste streams containing organic nitrogen compounds; the provision of such method that is environmentally compatible; the provision of such method that is less complex and less expensive than prior art methods; the provision of such method that effects extremely effective degradation of organic contaminants; the provision of such method that permits ammonia removal by stripping; the provision of such method that forms ammonium ions without the need for addition of acids or buffers; the provision of such method that facilitates ammonia recovery; and the provision of such method that facilitates the recycling or reuse of water.
- FIG. 1 is a graph of the chemical loading (represented by squares) and COD removal efficiency (represented by diamonds) for the fluidized bed reactor of Example 2;
- FIG. 2 is a graph of the chemical loading (represented by squares) and COD removal efficiency (represented by diamonds) for the fluidized bed reactor of Example 3.
- the method of this invention is directed to treatment of liquid aqueous waste streams that contain organic nitrogen compounds, such as liquid effluents from any of a variety of chemical syntheses as discussed, with an FBR.
- the present invention has been found to be extremely effective in treatment of mono-nitrile- or dinitrile-containing streams, and especially streams such as acrylonitrile stripper bottoms, or other purge water from acrylonitrile manufacturing plants, which contain the particularly toxic and degradation-resistant four-carbon dinitriles that produce high levels of nitrogen upon degradation.
- Such streams often contain more than about 50 ppm dinitriles based on weight.
- the construction of FBRs is well known.
- the FBR comprises a fluidized bed in a main column.
- the fluidized bed in turn comprises a particulate solid.
- suitable particulate solids are known in the industry and exemplary of such solids are sand, activated coconut carbon (such as available from Charcoal Filtration Media of Inglewood, Calif.) and granulated activated carbon (GAC).
- the particulate solid for use in the present method should be one that adsorbs organic nitrogen compounds, especially nitriles (particularly mono-nitriles and dinitriles), thereby to mitigate their toxicity.
- GAC has been found to be especially suitable for the instant process because it is able to support large quantities of biomass and has been found to be a surprisingly effective adsorbent for nitriles and some other wastewater contaminants. This is believed to be due to its high surface area per unit weight (1000 m 2 /gram) and the presence of activated chemical-binding sites. Thus, it provides chemical adsorption as a second mechanism of chemical removal from the liquid waste. As a result, the nitrogenous wastes are held in the reactor and the concentration of organic matter at the carbon-biomass interface is increased, stimulating microbial growth and chemical removal.
- the GAC adsorbs some toxic components, mitigating their toxic effects on the bacteria in the bioreactor and maintaining the biodegradation by bacteria at waste concentrations higher than those that can be treated with biotreatment systems.
- This advantage has been known for petroleum-type products such as toluene and the like.
- GAC is surprisingly effective in adsorbing toxic compositions such as nitriles and so its use results in substantial improvement in degradation efficacy and mitigation of toxicity.
- GAC also is beneficial for adsorbing surges in chemical loading which may occur in industrial applications. The surge loadings of chemicals are retained in the reactor until degraded by the microorganisms, resulting in more stable reactor performance and maintenance of a high quality effluent from the FBR.
- the particulate solid is coated with microorganisms capable of biodegrading the organic nitrogen compounds of interest in the waste stream to be treated.
- microorganisms capable of biodegrading the organic nitrogen compounds of interest in the waste stream to be treated.
- suitable materials for use as a particulate coating containing microorganisms may be obtained as mixed liquor suspended solids (MLSS) in activated sludge that is readily available from publicly operated treatment works that receive influent from sources other than residences (that is, that receive industrial wastes, especially a complex mix or variety of chemical wastes, as opposed to household wastes).
- MMS mixed liquor suspended solids
- a typical sludge of this type containing an uncharacterized consortium of bacteria was obtained from an activated sludge system from an AN producer and employed by the present inventors.
- Knowles employed a highly defined consortium of microorganisms and Kato et al. used a specific type of microorganism
- the present method is operable with a very generic, mixed microbial inoculum collected from industrial waste treatment systems.
- the main column of the FBR is equipped with a recycle line which recirculates water from the top of the bioreactor into the bottom of the bioreactor.
- This recycle line is equipped with an oxygen input for oxygenation of the recycle stream.
- the main column, and therefore the fluidized bed is not sparged with oxygen or any other gas.
- the only elemental oxygen injected into the fluidized bed is the oxygen (generally dissolved oxygen) that has been incorporated into in the recycle stream outside of the bed.
- the stream to be treated is generally an aqueous liquid containing organic nitrogen compounds, often toxic levels of organic nitrogen.
- aqueous liquid containing organic nitrogen compounds include purge water from acrylonitrile manufacturing plants, for instance, acrylonitrile stripper bottoms and derivatives of such stripper bottoms (i.e., acrylonitrile stripper bottoms that have undergone further treatment such as distillation or fractionation), and other nitrile-containing stream.
- "toxic" levels means that the 48 hr EC 50 for Ceriodaphnia dubia is 50% or less.
- the stream may contain a variety of nitriles and other compounds, such as particularly troublesome C 4 dinitriles such as succinonitrile, fumaronitrile, acrylonitrile and maleonitrile, as well as propionitrile, 3-cyanopyridine, acetonitrile, methacrylonitrile, acrylonitrile, crotononitrile, allyl cyanide, cyclopentadiene, cyanopentadiene, cyanobutadiene, pyrazine, cyanopropanal, acylamide, maleimide, benzonitrile, acrylic acid, acetic acid, oxyazole, hydrogen cyanide, and so forth.
- C 4 dinitriles such as succinonitrile, fumaronitrile, acrylonitrile and maleonitrile, as well as propionitrile, 3-cyanopyridine, acetonitrile, methacrylonitrile, acrylonitrile, crotononitrile, allyl
- Such compounds are normally found in the waste water produced in standard acrylonitrile synthesis.
- the present method has been found to be extremely effective in treating wastes of very high organic nitrogen content, such as in excess of about 300 total Kjeldahl nitrogen (TKN).
- TKN total Kjeldahl nitrogen
- the present method is even very effective in degrading organic nitrogen compounds present in concentrations above about 500 TKN, such as above 800 or 1,000 , and as high as 1,100 TKN or more.
- This invention will be capable of treating waste streams containing TKN values up to the point that the ammonia produced by microbial ammonification contains a high fraction of ionized ammonia, due to the low pH maintained by this invention, and free ammonia levels are below known acceptable toxicity limits for microorganisms.
- the treatment process may be run at continuous flow and may accommodate flow rates of, example, about 1.6 to about 6.8 kg COD/m 3 bed/day and thus even in excess of about 5 kg COD/m 3 bed/day.
- the stream is oxygenated, such as by means of an oxygen contactor chamber using pure or highly enriched oxygen, and then the highly oxygenated (dissolved oxygen) liquid is fed to the fluidized bed of the FBR, where aerobic microbial degradation occurs.
- This oxygenation might take place in the influent stream, but preferably takes place in the recycle line.
- the fluidized bed and main column are not aerated or sparged with gas.
- carbon dioxide produced by microbial respiration in the microbial degradation of the organic nitrogen compounds is not stripped out as in conventional technologies such as the activated sludge techniques of Kato et al. and the continuously aerated fixed film reactors of Knowles. Accordingly, the carbon dioxide may accumulate to extremely high levels, even to the point of effervescence when the feed contains high levels of degradable organics.
- the effluent from the fluidized bed therefore is highly carbonated, providing substantial buffering of the effluent according to the reaction CO 2 +H 2 O ⁇ HCO 3 - +H + .
- the increase in carbon dioxide in the new method forces the reaction to the right, decreasing pH in mitigation of the pH increasing tendency of the high ammonia content.
- the toxic ammonia is converted to the relatively nontoxic ammonium ion and so it is possible to accommodate higher ammonia levels without high toxicity.
- This new method avoids undesirably high pH and maintains neutral pH without additional steps or additives.
- the lowering of the pH resulting from high levels of carbon dioxide in FBRs is beneficial for maintaining neutral pH in applications (such as from about 6 to about 8, preferably about 6.7 to about 7.2, more preferably about 6.7 to about 7.1, especially about 6.8 to about 7) where the pH of liquid wastes would normally increase as a result of microbial degradation of chemicals, such as the microbial degradation of organic acids.
- the resulting effluent of high dissolved ammonia concentration (in the form of the ammonium ion) may then be routed for ammonia removal downstream.
- the removal may be carried out by any of many standard mechanisms such as an ammonia stripper. Because the ammonia is neutralized by the carbon dioxide to carbonate buffering mechanism rather than by addition of phosphoric acid or the like, ammonia stripping is simple and straight forward.
- the effluent does not contain high levels of exogenous acid to control pH that would interfere with ammonia stripping and so the carbon dioxide may be readily removed, thereby raising the pH of the effluent, and facilitating the ammonia stripping.
- complex, capital intensive, and expensive biological nitrification and denitrification as described in the Jeris patent are unnecessary.
- the absence of exogenous acid also facilitates recycling of water.
- the organic nitrogen compounds in the waste stream are nearly completely degraded by the method of this invention, resulting in a treated waste stream nearly free of such compounds.
- the degradation is so nearly complete that the COD reduction is greater than 80%, typically greater than about 90% or even 95%.
- COD reduction in excess of about 97% or 98% has been achieved.
- toxicity reduction has been found to be substantial as well.
- the influent waste water may be extremely toxic (for example, it may have a 48 hr EC 50 for Ceriodaphnia dubia well below the toxic level of 50%, normally less than a percent, even less than a tenth of a percent)
- the effluent is relatively nontoxic.
- the 48 hr EC 50 for Ceriodaphnia dubia of the effluent stream may be over one hundred times higher, often more than even five hundred times higher than that of the influent stream.
- the 48 hr EC 50 for Ceriodaphnia dubia of the effluent stream is well above 50%, such as more than 70% and even may be greater than about 80%.
- non-chlorinated water (20 L) was added to the main column of a laboratory scale FBR followed by addition of granulated activated carbon (approximately 2.8 kg) to a settled bed depth of 0.6 meters.
- granulated activated carbon approximately 2.8 kg
- water was passed upward through the carbon bed at a velocity sufficient to expand the bed beyond the point at which the frictional drag was equal to the net downward force exerted by gravity.
- the bed was fluidized at a recycle flow rate of 1.0-1.2 gpm, to give an upflow velocity of 46-55 cm/min and a hydraulic recycling rate of 466-560 / min/m 2 . This produced fluidization of the carbon bed to a height of 0.9 m (50% bed expansion).
- the volume of the carbon bed was 7.2 liters.
- AN Acrylonitrile
- the raw waste had a pH of about 5.2 and during start-up was adjusted to pH 7.0. Since the raw feed contained sufficient nitrogen and trace elements to support microbial growth, no additional supplements were added to the wastewater feed.
- the microbial inoculum was added to the top of the reactor column and oxygenation was initiated.
- the microbial inoculation was carried out with inoculum that was a mixed microbial population from secondary return sludge from an activated sludge system from a waste treatment plant of an AN producer, and sludge from the activated sludge systems at two other industrial waste treatment plants.
- Sludge samples were homogenized by low-speed mixing in a blender before addition to the FBR column to prevent clumping of the biomass and to promote better adherence of the sludge to the carbon support.
- the GAC bed was inoculated with activated sludge (11) and the sludge was allowed to recirculate for 24 hours prior to start-up of continuous influent feed.
- the FBR was ⁇ batch ⁇ fed for one week by adding AN wastewater (0.5l) to the reactor.
- the batch quantity of feed served as an additional food supply for the microbial inoculum as the biomass acclimated to the FBR.
- the FBR effluent was clear of recirculating solids (unattached inoculum) and significant levels of oxygen uptake were detected.
- a continuous feed of AN wastewater to the FBR was begun at a flow rate of 1 ml/min.
- Adsorption of wastestream chemicals onto the carbon support served as a concentrated food source to promote microbial attachment and growth on the carbon during the initial start-up phase after microbial inoculation.
- pre-adsorbing chemicals to the active sites on the GAC would increase the probability that disappearance of specific carbon-adsorbable wastestream components alter in the study was due to microbial degradation, rather than selective carbon adsorption of the compounds.
- the influent feed was pumped into the recycle flow and pure oxygen was metered into the recycle stream using a mass flow controller (Model VCD 1000, Porter Instrument Co., St. Louis, Mo.).
- the recycle stream then flowed to the FBR oxygenation column and was thoroughly mixed.
- the total oxygenated recycle water (wastewater feed plus recycle water) exited the oxygen contact column and flowed into the bottom of the reactor column.
- Dissolved oxygen (DO) probes were used to detect levels of oxygen both at the influent flow (base of carbon bed) and at the recycle port (top of the reactor carbon) in order to measure oxygen use in the FBR and help in the control of DO at the desired levels.
- Dissolved oxygen levels in the FBR headspace were maintained at 2-4 mg O 2 /l throughout the study.
- the carbon biocarrier provided a vast and irregular surface which promoted microbial attachment and growth, resulting in an increase in height of the fluidized bed.
- the initial AN wastewater flow rate to the reactor was 1 ml/min during the start-up phase. After a 7 day acclimation period, the influent flow rate was increased to 1.5 ml/min and held for another 7 days. This flow rate corresponded to the chemical loading level of 3.0 kg COD/m 3 bed/day based upon an average COD of 10,500 mg/l for the raw waste.
- the chemical load to the system was increased to 6.1 kg COD/m 3 bed/day (3 ml/min), and was held for 3 days.
- a third step-change in flow rate to 6 ml/min gave a chemical loading rate of 12.2 kg COD/m 3 bed/day. This influent flow rate was held for 6 days before the last step-change occurred.
- the final chemical loading rate to the FBR was 16.0 kg COD/m 3 bed/day and was delivered to the reactor by addition of (8 ml/min) of AN wastewater.
- Effluent samples discharged from the FBR were taken from the effluent port at a minimum of three times each week for COD analysis.
- the influent feed to the FBR was analyzed for COD each time a new feed tank was used.
- Samples were filtered through a 0.45 ⁇ m filter and analyzed using an EPA approved analytical method for measuring the amount of organic matter in the water. Colorimetric determination of COD was performed with a commercial HACH test kit (HACH Analytical Methods Company, Loveland, Colo.).
- Effluent samples for TOC analysis were also collected three times each week.
- Effluent from the FBR was collected at least twice each week, and at each flow rate change, for determination of ammonia content (NH 3 --N) and total Kjeldahl nitrogen (TKN).
- a sample (150 ml) was filtered 0.45 ⁇ m and stored at 4° C. until shipped to a laboratory for analysis.
- Biomass growing on the carbon support matrix expanded the carbon particle diameter as the influent chemical loading was increased. Excess biomass that detached from the GAC or was stripped off the BCD floated out of the main FBR column into the sludge collection trap. In addition, small particles of biomass that remained suspended in the water passed out of the system through the effluent port.
- Effluent samples were taken for nitrile and acid analysis at a minimum of twice each week, and at each chemical loading rate change. Each analysis consisted of duplicate filtered (0.45 ⁇ m) effluent samples (40 ml each) placed in glass vials and stored at 4° C. The samples were analyzed by the methods described above for the AN process wastewater.
- Nitrile compounds in extracts were characterized by GC/MS using analytical methods described above for analysis of influent and effluent water. The limit of detection was (5 ⁇ g nitrile/g carbon).
- the gas emitted from the top of the reactor column was monitored during steady-state performance of the FBR. Samples were collected over a 10 hour time period by trapping the gas in a summa vessel. After collection of the samples, the ammonia concentration was determined using a Corning Model 250 pH meter with a Corning Ammonia combination electrode.
- the measurement of COD and TOC began 5 days after the inoculation of the carbon biocarrier.
- the chemical loading and COD removal efficiency found is shown in FIG. 1.
- the COD of the FBR effluent was below 5 mg/l during the microbial acclimation period.
- Measurement of effluent TOC during the 12-day acclimation period showed a greater than 99% efficiency of TOC removal.
- the reactor had a COD and TOC removal efficiency of 99%.
- the COD loading rate to the reactor was doubled at day 16 to 12.5 kg COD/m 3 bed/day.
- the loading increase was followed by an increase in the effluent COD to (100 mg/l ) and after 3 days the effluent COD was (290 mg/l ) and TOC was (100 mg/l ), representing a 97% rate of COD and TOC removal.
- the reactor was able to tolerate a 2-fold loading increase above design loading rate.
- the COD loading to the reactor was increased to 16.0 kg COD/m 3 bed/day on day 21.
- the FBR responded to the maximum loading rate by an immediate downturn in removal efficiency.
- the COD levels in the FBR effluent increased sharply over a 4-day period.
- Removal efficiency for COD decreased to 58% by day 25 showing that the FBR was not able to withstand the 16.0 kg COD/m 3 bed/day loading rate.
- the immobilized bacteria were not oxygen limited since the DO at the effluent port remained at the 2-4 mg/l level.
- the DO differential did decrease to 2 mg/l, which suggests that the higher chemical concentrations may have resulted in some toxicity to chemical-degrading bacteria in the FBR resulting in lower oxygen utilization.
- Example 2 This study evaluated the long-term operation and performance stability of the FBR for treating AN wastewater.
- a lab-scale FBR was prepared in accordance with the procedure of Example 1, above, except that a mixed microbial population from only one of the activated sludges used in the pre-adsorption was used as inoculum.
- the general procedures of Example 2 were repeated except as follows.
- This FBR study began by acclimating the reactor to a 1.6 kg COD/m 3 bed/day (1 ml/min) influent flow for 10 days.
- the average COD for the raw AN wastewater in this study was 8,000 mg/l.
- the chemical load to the system was increased to 3.2 kg COD/m 3 bed/day (2 ml/min).
- This chemical loading rate was maintained for 20 days before the influent flow rate was increased to 5.0 kg COD/m 3 bed/day (3 ml/min).
- the 5.0 kg COD/m 3 bed/day loading rate had been maintained for 16 days, representing 9.5 hydraulic resident times (HRTs)
- the influent flow was increased to the maximum rate of 6.8 kg COD/m 3 bed/day (4 ml/min).
- the chemical loading rate was decreased to 4.8 kg COD/m 3 bed/day and remained at this loading rate for the remainder of the study.
- Biomass measurements were carried out. Biomass measurements also were determined in this study from carbon samples taken at the top and the bottom of the carbon support bed. Measurements for biomass attached to the GAC were made using a gravimetric/heat volatilization method. Biomass measurements were used to determine total biomass present during each chemical loading rate.
- the FBR was run at steady-state operation an additional 2 months (days 62-125).
- end-point samples of the effluent were analyzed by gas chromatography/mass spectroscopy (GC/MS), electrospray MS, and capillary zone electrophoresis (CZE) for identification of the organic compound(s) present in the effluent.
- GC/MS gas chromatography/mass spectroscopy
- electrospray MS electrospray MS
- CZE capillary zone electrophoresis
- FIG. 2 A graphical presentation of chemical loading (COD) and removal efficiency is shown in FIG. 2.
- concentrations of COD and TOC in the FBR effluent at the time of start-up were 100 mg/l and 57 mg/l, respectively.
- Initial COD and TOC levels were present due to the pre-adsorption phase before the carbon support was inoculated with microorganisms.
- the COD of the effluent remained below 80 mg/l and TOC was low (less than 20 mg/l ). This represented a removal efficiency of 99% during the reactor start-up period.
- the loading rate was increased to 3.2 kg COD/m 3 bed/day (60 hrs HRT).
- the FBR received a temporary ⁇ shock-load ⁇ (for approximately 18 hours) of 12.5 kg COD/m 3 bed/day on Day 47. This was caused by switching to a new drum of stripper bottoms waste containing a high COD lead (21,000 mg/l ) as influent feed.
- the COD of the FBR effluent increased to 305 mg/l and TOC was 171 mg/l immediately after the shock-load.
- the FBR was flushed with clean water (8 l) to remove the extra carbonaceous load and feed to the reactor was shut off for 2 days to allow the biomass to recover from the shock-load.
- the new feed was diluted with water to a concentration of 8,000-9,000 mg/l of COD, which is representative of the normal concentration of AN stripper bottoms waste.
- the TKN of the raw waste used for the first 50 days of the feasibility study was 1,100 mg/l, and the ammonia nitrogen content was 65 mg/l.
- the TKN of the influent feed for days 51-70 of the study was 800 mg/l.
- the level of NH 3 --N in the FBR steadily increased to a maximum concentration of 797 mg/l on day 49.
- the chemical shock-load that occurred at day 47 elevated the NH 3 --N content in the effluent.
- the 40% decrease in effluent NH 3 --N concentration (day 50) after the shock-load was attributed to flushing of the FBR with clean water to remove potential toxic loads of waste constituents that had entered the system during the chemical shock.
- the FBR containing GAC had the potential to adsorb nitrile and pyridine compounds in order to promote microbial degradation to ammonia. However, the adsorptive capacity was low, as determined by reported specific carbon adsorption isotherms for these compounds. Mass balance analysis for the major organic constituents in the AN waste required the periodic analysis of the carbon to determine if removal of the organics from the effluent was due to selective removal by adsorption onto the GAC.
- Pre-adsorbing the carbon with AN wastewater prior to microbial inoculation allowed for low-levels of the nitriles and 3-cyanopyridine to accumulate on the GAC.
- no detectable quantities of succinonitrile were present on the carbon indicating that the initial 578 ⁇ g/g of succinonitrile present on GAC at reactor start-up was removed.
- other nitrile compounds were found not to accumulate of the GAC.
- the mass of GAC in the FBR and the chemical loading of 3-cyanopyridine can be used to calculate the expected residues on the GAC if chemical adsorption were the sole route of removal for 3-cyanopyridine.
- the FBR contained approximately 2,800 grams of GAC and the concentration of 3-cyanopyridine on the carbon support at day 64 was (178 ⁇ g/g carbon). Therefore, a total of 498 mg of 3-cyanopyridine was adsorbed onto the bed 64 days after start-up. Since the concentration of 3-cyanopyridine in the AN stripper bottoms waste was 75 mg/l, a total of 15 grams of the chemical had been loaded into the reactor by day 64.
- the theoretical accumulation of individual nitrile components in the FBR was determined by calculating the concentration of chemical flowing into the reactor minus the concentration of chemical flowing out of the reactor.
- the expected concentration of nitriles and 3-cyanopyridine present in the effluent at day 17 would be: 1,278 mg/L succinonitrile, 2.49 mg/L acrylonitrile, 262 mg/L fumaronitrile, 53 mg/L 3-cyanopyridine.
- analysis of the FBR effluent during the acclimation period revealed no nitriles or 3-cyanopyridine present.
- the FBR produced stable COD and TOC removal efficiencies ranging from 99% (1.6 kg COD/m 3 bed/day) to 94% (6.7 kg COD/m 3 bed/day). This study showed that more than 97% of the COD and TOC of the wastewater could be removed consistently during steady-state operation of the reactor at a chemical loading rate of 5.0 kg COD/m 3 bed/day.
- Biodegradation of AN wastewater containing high levels of nitriles produced concentrations of ammonia ranging from 400 to 800 mg/l. Levels of ammonia above 300 mg/l can have severe toxic effects on the catabolic activities of microorganisms.
- the toxicity of aqueous ammonia depends primarily on the pH of the water since only the un-ionized molecule (NH 3 as opposed to NH 4 +) is toxic. At a pH of 7.0 or less, microbes can tolerate high levels of total ammonia since most is present as NH 4 +.
- the FBR maintained a stable pH of 6.7-6.8 due to the large biogeneration of carbon dioxide from biodegradation of the stripper bottoms waste.
- the GAC used in the FBR provided a vast surface area for biological growth, and contributed to the ability of the reactor to sustain high biomass levels ranging from up to 47,000 mg/l. These biomass concentrations were five to ten fold higher than can be achieved in conventional activated sludge systems (CASS).
- CASS activated sludge systems
Abstract
Description
______________________________________ Characteristic Concentration (mg/l) ______________________________________ Succinonitrile 1,800 Fumaronitrile 370 Acrylonitrile 3.5 Maleonitrile 110 Unidentified nitrile 160 3-Cyanopyridine 75 Cyanopropionaldehyde 200 Acetic Acid 2,400 Acrylic Acid 2,800 ______________________________________
______________________________________ Characteristic Concentration (mg/l) ______________________________________ COD 8,000-10,500 TOC 2,700-3,500 TKN 800-1,100 or more NH.sub.3 100TSS 20 ______________________________________
______________________________________ Chemical Loading (kg COD/m.sup.3 TKN NH.sub.3 --N Days bed/day) HRT (hr) (mg/l) (mg/l) ______________________________________ 1 1.6 120 64 45 7 1.6 120 463 432 11 1.6 120 511 418 18 3.2 60 546 546 21 3.2 60 527 588 24 3.2 60 637 555 25 3.2 60 665 672 32 5.0 40 648 672 38 5.0 40 675 666 43 5.0 40 746 751 49 5.0 40 .sup. 814.sup.1 797 50 5.0 40 480 477 54 6.8 30 434 424 58 6.8 30 492 483 62 6.8 30 582 553 68 6.8 30 619 606 69 6.8 30 561 562 ______________________________________ .sup.1 A surgeload of chemical occurred on day 47 causing elevated TKN an ammonia levels in the effluent.
______________________________________ Chemical Loading (kg COD/ Biomass Days m.sup.3 bed/day) HRT (hr) (mg/l) ______________________________________ 18 1.6 120 16,000 32 3.2 60 23,000 47 5.0 40 33,500 62 6.8 30 47,000 ______________________________________
______________________________________ Days After Fumaroni- Cyano- Start-Up Succinonitrile trile pyridine ______________________________________Control 0 0 0 Pre- 278 61 127 adsorption 17 .sup. ND.sup.2 5 117 23 ND ND 149 37 ND 26 254 45 ND 14 139 64 ND 8 178 ______________________________________ .sup.1 Concentration values are ug compound/g carbon. Estimated limit of detection is 5 ug/g. .sup.2 ND = not detected.
______________________________________ Days After Chemical.sup.1 Succin- Fumaroni- Acrylon 3-Cyano- Start-up Loading onitrile trile itrile pyridine ______________________________________ 1 1.6 4.1 ND ND ND 2 1.6 4.7 ND ND ND 6 1.6 ND ND ND ND 17 1.6 NDND ND ND 20 3.2 ND ND ND ND 23 3.2 ND ND ND ND 24 3.2 ND ND ND ND 31 3.2 ND ND ND ND 37 5.0 ND ND ND ND 45 5.0 NDND ND ND 50 5.0 ND ND ND ND 52 5.0 ND ND ND ND 56 6.8 ND ND ND ND 62 6.8 ND ND ND ND 69 6.8 ND ND ND ND 71 6.8 ND ND ND ND ______________________________________ .sup.1 Succinonitrile, fumaronitrile and 3cyanopyridine concentrations ar reported in mg/L, with a limit of detection of 1 mg/L. Acrylonitrile concentrations are reported in ug/L, with a limit of detection of 100 ug/L. .sup.2 Chemical loading rates are reported as kg COD M.sup.-3 bed day.sup.-1.
Claims (39)
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US08/458,946 US5540840A (en) | 1995-06-02 | 1995-06-02 | Use of fluidized bed reactors for treatment of wastes containing organic nitrogen compounds |
AU57407/96A AU5740796A (en) | 1995-06-02 | 1996-05-10 | Use of fluidized bed reactors for treatment of wastes contai ning organic nitrogen compounds |
PCT/US1996/006706 WO1996038388A1 (en) | 1995-06-02 | 1996-05-10 | Use of fluidized bed reactors for treatment of wastes containing organic nitrogen compounds |
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Cited By (13)
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US5863750A (en) * | 1996-12-18 | 1999-01-26 | Cytec Tech Corp | Methods for the detoxification of nitrile and/or amide compounds |
US6060265A (en) * | 1996-12-18 | 2000-05-09 | Cytec Technology Corporation | Methods for the detoxification of nitrile and/or amide compounds |
US6171503B1 (en) | 1998-03-16 | 2001-01-09 | Dalhousie University | Use of tetraphenyloborate for extraction of ammonium ions and amines from water |
US20020189998A1 (en) * | 2000-04-03 | 2002-12-19 | Haase Richard A. | Processes and apparatus for potable water purification that include bio-filtration, and treated water from such processes and apparatus |
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US8486359B2 (en) | 2011-07-25 | 2013-07-16 | Coskata, Inc. | Ammonium recovery from waste water using CO2 acidified absorption water |
US8580219B2 (en) | 2011-07-25 | 2013-11-12 | Coskata, Inc. | Ammonium recovery methods |
US8685246B2 (en) | 2010-09-20 | 2014-04-01 | American Water Works Company, Inc. | Simultaneous anoxic biological phosphorus and nitrogen removal with energy recovery |
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US6132985A (en) * | 1996-12-18 | 2000-10-17 | Cytec Technology Corporation | Methods for the detoxification of nitrile and/or amide compounds |
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US8486359B2 (en) | 2011-07-25 | 2013-07-16 | Coskata, Inc. | Ammonium recovery from waste water using CO2 acidified absorption water |
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US11358885B2 (en) * | 2018-04-04 | 2022-06-14 | Bluestar Adisseo Nanjing Co., Ltd. | Method and device for treating acrolein reactor wastewater |
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